• Title/Summary/Keyword: Chiral catalyst

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Cyanosilylation of Carbonyl Compounds Catalyzed by Potassium L-Aspartate

  • George, Soney C.;Kim, Sung-Soo;Kim, Ho-Sub
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2431-2434
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    • 2007
  • Potassium L-aspartate has been used as a catalyst for the cyanosilylation of carbonyl compounds producing corresponding cyanohydrin trimethylsilyl ethers in excellent yield of up to 98%. Although the catalyst is chiral, the enantioselectivities observed are generally poor except for one case, α-naphthaldehyde, 89% ee.

Hydrolytic Kinetic Resolution of Racemic Alkyl-glycidyl Derivatives by using Dimeric Chiral Salen Catalyst Containing Ga, In and TlCl3 (염화갈륨, 인듐 및 탈륨 함유 이분자형 키랄 살렌 촉매에 의한 라세믹 알킬 글리시딜레이트 유도체의 비대칭 가수분해반응)

  • Shin, Chang-Kyo;Rahul, B. Kawthekar;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.18 no.3
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    • pp.218-226
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    • 2007
  • The stereoselective synthesis of chiral terminal epoxides is of immense academic and industrial interest due to their utility as versatile starting materials as well as chiral intermediates. In this study, new dinuclear chiral Co (salen) complexes bearing gallium-, indium- and tallium-chloride have been synthesized and characterized. The mass and EXAFS spectra provided the direct evidence of formation of dinuclear complex. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of various terminal epoxides having ether or ester groups by hydrolytic kinetic resolution technology. The easily prepared dimeric complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ nucleophile, providing enantiomerically enriched terminal epoxides (> 99% ee). The dimeric structured chiral salen showed remarkably enhanced reactivity and may be employed substantially lower loadings than its monomeric analogues. The system described in this work is very efficient for the synthesis of chiral epoxide and 1,2-diol intermediates

Asymmetric Ring Opening Reaction of Racemic Epoxides by Polymeric Chiral Salen Catalyst containing Metal Salts (금속염 함유 고분자형 키랄 살렌촉매에 의한 라세믹 에폭사이드의 광학선택적 비대칭 고리열림반응)

  • Lee, Kwang Yeon;Rahul, B. Kawthekar;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.18 no.6
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    • pp.562-567
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    • 2007
  • The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their use as versatile starting materials as well as chiral intermediates. In this study, new polymeric chiral Co(salen) complexes bearing tallium (III)chloride and iron (III)chloride (ferric chloride) have been synthesized and characterized. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of various terminal epoxides using water and phenol derivatives as nucleophiles. The easily prepared polymeric complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ and phenol nucleophiles, providing enantiomerically enriched terminal epoxides (> 98% ee). The system described in this work is very efficient for the synthesis of chiral epoxide, 1,2-diol and ${\alpha}$-aryloxy alcohol intermediates.

Enantioselective Epoxide Synthesis on the Chiral Salen Catalyst having a Transitional Metal Salt (전이금속염 함유 키랄 살렌 촉매에 의한 광학선택적 에폭사이드의 합성)

  • Guo, Xiao-Feng;Kawthekar, Rahul B.;Kim, Geon-Joong
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.769-776
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    • 2008
  • The stereoselective synthesis of chiral terminal epoxide is of immense interest due to their utility as versatile starting materials as well as chiral intermediates. In this study, new chiral Co(salen) complexes bearing cobalt(II) chloride, iron(III) chloride and zinc(II) nitrate have been synthesized and characterized. The mass and EXAFS spectra provided the direct evidence of formation of complex. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of terminal epoxides such as styrene oxide and phenylglycidylether by hydrolytic kinetic resolution technology and for the synthesis of glycidyl buthylate. The easily prepared complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ nucleophile, providing enantiomerically enriched terminal epoxides (>99% ee). The newly synthesized chiral salen showed remakablely enhanced reactivity with substantially low loadings. The system described in this work is very efficient for the sinthesis of chiral epoxide and 1,2-diol intermediates.

Synthesis of Highly Enantiomerically Enriched Arenesulfonic Acid 2-Hydroxy Esters via Kinetic Resolution of Terminal Epoxides (속도론적 분할법을 통한 말단 에폭사이드로부터 고광학순도의 아렌술폰산 2-하이드록시 에스터의 합성)

  • Lee, Yae Won;Yang, Hee Chun;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.27 no.5
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    • pp.490-494
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    • 2016
  • This paper describes the very efficient and highly enantioselective ring opening of terminal epoxides with alkyl and arene sulfonic acid. The dinuclear chiral (salen) Co complexes bearing Lewis acids of Al, Ga and In catalyze the reaction enantioselectively in the presence of tetrabutylammonium chloride using tert-butyl methyl ether as a solvent. The variation of the anion of the tetra butyl ammonium salt has significant impact on the reactivity and selectivity of the asymmetric ring opening of phenyl glycidyl ether with p-toluenesulfonic acid. The order of reactivity and selectivity was found to be $Cl^-$ > $l^-$ > $Br^-$ > $OH^-$. Strong synergistic effects of the different Lewis acid centers of Co-Al, Co-Ga and Co-In complexes were observed in the catalytic process. The dinuclear chiral salen catalyst containing $AlCl_3$ was found to be most active and highly enantioselective (91% ee).